JP4961786B2 - Transparent conductive film and transparent conductive film using the same - Google Patents
Transparent conductive film and transparent conductive film using the same Download PDFInfo
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- JP4961786B2 JP4961786B2 JP2006074449A JP2006074449A JP4961786B2 JP 4961786 B2 JP4961786 B2 JP 4961786B2 JP 2006074449 A JP2006074449 A JP 2006074449A JP 2006074449 A JP2006074449 A JP 2006074449A JP 4961786 B2 JP4961786 B2 JP 4961786B2
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- 229910052751 metal Inorganic materials 0.000 claims description 50
- 239000002184 metal Substances 0.000 claims description 50
- 229910052709 silver Inorganic materials 0.000 claims description 30
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- 238000004544 sputter deposition Methods 0.000 claims description 27
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 229910052725 zinc Inorganic materials 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 13
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- 229910007604 Zn—Sn—O Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 317
- 239000007789 gas Substances 0.000 description 25
- 239000011701 zinc Substances 0.000 description 21
- 239000003513 alkali Substances 0.000 description 17
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- 239000004973 liquid crystal related substance Substances 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 229910001887 tin oxide Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910007717 ZnSnO Inorganic materials 0.000 description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- 229910002708 Au–Cu Inorganic materials 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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Description
本発明はプラズマディスプレイの電磁波遮蔽フィルターや液晶ディスプレイの透明電極などに利用できる透明導電膜に関する。 The present invention relates to a transparent conductive film that can be used for an electromagnetic wave shielding filter of a plasma display, a transparent electrode of a liquid crystal display, and the like.
透明導電膜は、高い導電性（例えば、１×１０-3Ωｃｍ以下の比抵抗）と、可視光領域での高い透過率とを有するため、太陽電池、液晶表示素子、その他、各種の受光素子等の電極として利用されるほか、自動車窓ガラスや、建築物の窓ガラス等に用いる熱線反射膜、各種の帯電防止膜、冷凍ショーケースなどの防曇用の透明発熱体としても利用されている。 Since the transparent conductive film has high conductivity (for example, a specific resistance of 1 × 10 −3 Ωcm or less) and high transmittance in the visible light region, it is a solar cell, a liquid crystal display element, and other various light receiving elements. It is also used as a transparent heating element for anti-fogging, such as heat ray reflective films used for automobile window glass, building window glass, various antistatic films, refrigeration showcases, etc. .
透明導電膜には、アンチモンやフッ素がドーピングされた酸化錫（ＳｎＯ2）膜、アルミニウムやガリウムがドーピングされた酸化亜鉛（ＺｎＯ）膜、錫がドーピングされた酸化インジウム（Ｉｎ2Ｏ3）膜などが広範に利用されている。特に、錫がドーピングされた酸化インジウム膜、すなわちＩｎ2Ｏ3−Ｓｎ系膜は、ＩＴＯ（Indium Tin Oxide）膜と称され、低抵抗の透明導電膜が容易に得られることから、ＬＣＤをはじめとして、種々のデバイスに広く用いられている。ＩＴＯ膜は、スパッタリング法で室温で基板上に成膜すると、膜厚２００ｎｍで表面抵抗２５Ω／□程度（比抵抗で約５×１０-4Ωｃｍ）の導電性を示す。 Examples of transparent conductive films include tin oxide (SnO 2 ) films doped with antimony and fluorine, zinc oxide (ZnO) films doped with aluminum and gallium, and indium oxide (In 2 O 3 ) films doped with tin. Is widely used. In particular, an indium oxide film doped with tin, that is, an In 2 O 3 —Sn-based film is called an ITO (Indium Tin Oxide) film, and a low-resistance transparent conductive film can be easily obtained. Are widely used in various devices. When an ITO film is formed on a substrate at room temperature by a sputtering method, the film has a film thickness of 200 nm and exhibits a surface resistance of about 25 Ω / □ (specific resistance is about 5 × 10 −4 Ωcm).
一方で、透明酸化物薄膜と金属薄膜の積層によって構成された透明導電膜も提案されている。一般的に、室温で成膜した膜厚１００ｎｍ程度のＩＴＯ膜の表面抵抗が５０Ω／□前後であるのに対し、膜厚５０〜１００ｎｍの上記積層膜の表面抵抗は、銀系合金薄膜の膜厚にもよるが、１５Ω／□以下とすることも可能であり、場合によっては１０Ω／□以下とすることも可能である。 On the other hand, a transparent conductive film composed of a laminate of a transparent oxide thin film and a metal thin film has also been proposed. In general, the surface resistance of an ITO film having a thickness of about 100 nm formed at room temperature is around 50 Ω / □, whereas the surface resistance of the laminated film having a thickness of 50 to 100 nm is a film of a silver-based alloy thin film. Although it depends on the thickness, it may be 15Ω / □ or less, and may be 10Ω / □ or less in some cases.
例えば、（１）銀層を酸化インジウム膜（ＩＯ）層で挟んだ構造（ＩＯ／Ａｇ／ＩＯ）、（２）銀層をＩＴＯ膜層で挟んだ構造（ＩＴＯ／Ａｇ／ＩＴＯ）、（３）銀層をセリウム添加酸化インジウム膜（Ｉｎ−Ｃｅ−Ｏ、ＩＣＯ）で挟んだ構造（ＩＣＯ／Ａｇ／ＩＣＯ）（特開平９−１７６８３７号公報）、（４）銀層をＧａ添加ＺｎＯ膜（ＧＺＯ）層で挟んだ構造（ＧＺＯ／Ａｇ／ＧＺＯ）などが提案されている。
ＩＯ／Ａｇ／ＩＯ、やＩＴＯ／Ａｇ／ＩＴＯは、耐薬品性に優れてはいるものの、室内放置により白色欠点が生じる。
また（１）〜（３）はＩｎ系の薄膜を使用しており、希少金属であるＩｎ資源の枯渇の問題が深刻となっていることと、Ｉｎ金属の人体に及ぼす毒性の問題があり環境に易しくないなどの問題点があるとされている。一方、ＧＺＯ／Ａｇ／ＧＺＯは、環境に優しく資源も豊富なＺｎ系材料を利用しており、耐湿性も良好である。しかし、耐薬品性が不充分であるという欠点がある。
Although IO / Ag / IO and ITO / Ag / ITO are excellent in chemical resistance, white defects occur when left indoors.
In addition, (1) to (3) use an In-based thin film, the problem of depletion of In resources, which are rare metals, is serious, and there is a problem of toxicity of In metal on the human body. It is said that there are problems such as not easy. On the other hand, GZO / Ag / GZO uses a Zn-based material that is environmentally friendly and abundant in resources, and has good moisture resistance. However, there is a drawback that the chemical resistance is insufficient.
本発明は、毒性があってしかも希少金属であるＩｎ金属を利用せず、安価で資源的に豊富な元素で酸化物膜を構成し、耐湿性や耐薬品性にも優れた、酸化物膜と金属膜とから構成される透明導電膜と、これを用いた透明導電性フィルムの提供とを課題とする。 The present invention is an oxide film that does not use toxic and rare In metal, and is composed of an inexpensive and resource-rich element and has excellent moisture resistance and chemical resistance. It is an object to provide a transparent conductive film composed of a metal film and a transparent conductive film using the transparent conductive film.
上記課題を解決する本発明の第１の発明によれば、複数層から構成される透明導電膜であり、構成層が、銀若しくは銀を主成分とする合金からなる金属膜と、該金属膜との両面に設けられたＳｎとＺｎとＯとを主成分とする非晶質のＺｎ−Ｓｎ−Ｏ系酸化物膜を含み、かつ該Ｚｎ−Ｓｎ−Ｏ系酸化物膜は、酸化物焼結体ターゲットを用いたスパッタリングにより形成され、Ｓｎの含有量が、ＳｎとＺｎの総和に対して１０〜９０原子％であることを特徴とする透明導電膜が提供される。 According to 1st invention of this invention which solves the said subject, It is a transparent conductive film comprised from multiple layers, and a constituent layer is a metal film which consists of silver or an alloy which has silver as a main component, and this metal film comprises amorphous Zn-Sn-O-based oxide film mainly composed of Sn and Zn and O provided on both sides of the, and the Zn-Sn-O-based oxide film, the oxide sintered A transparent conductive film is provided which is formed by sputtering using a combined target and has a Sn content of 10 to 90 atomic% with respect to the total of Sn and Zn .
そして、本発明の第２の発明によれば、第１の発明において、前記透明導電膜の少なくとも片面にａ−ＺＳＯ膜と異なる酸化物膜が積層されたことを特徴とする透明導電膜が提供される。 According to a second aspect of the present invention, there is provided the transparent conductive film according to the first aspect , wherein an oxide film different from the a-ZSO film is laminated on at least one surface of the transparent conductive film. Is done .
そして、本発明の第３の発明によれば、ａ−ＺＳＯ膜、銀を主成分とする金属膜、ａ−ＺＳＯ膜、銀を主成分とする金属膜、ａ−ＺＳＯ膜の順に積層されることを特徴とする透明導電膜が提供される。 According to the third aspect of the present invention , an a-ZSO film, a metal film containing silver as a main component, an a-ZSO film, a metal film containing silver as a main component, and an a-ZSO film are stacked in this order. A transparent conductive film is provided .
そして、本発明の第４の発明によれば、第１〜３の発明において、透明導電膜のうちの少なくとも二つを組み合わせて構成されていることを特徴とする透明導電膜が提供される。 And according to 4th invention of this invention , in 1st-3rd invention, the transparent conductive film characterized by combining at least two of the transparent conductive films is provided .
そして、本発明の第５の発明によれば、第１の発明において、ａ−ＺＳＯ膜が、ＧａとＡｌのうちの少なくとも１種類を該酸化物膜中の全金属の総和に対して５０原子％以下の割合で含有することを特徴とする透明導電膜が提供される。 According to the fifth aspect of the present invention, in the first aspect , the a-ZSO film comprises at least one of Ga and Al at 50 atoms with respect to the total of all metals in the oxide film. The transparent conductive film characterized by containing in the ratio of% or less is provided.
そして、本発明の第６の発明によれば、第１〜５のいずれかの発明において、合金膜が銀を主成分として、パラジウム、金、白金、銅からなる群から選ばれる１種以上の金属を、銀との合量に対して０．１〜１０原子％の割合で含む合金膜であることを特徴とする透明導電膜が提供される。 And according to the sixth invention of the present invention, in any one of the first to fifth inventions, the alloy film is composed of silver as a main component, and one or more kinds selected from the group consisting of palladium, gold, platinum, and copper. A transparent conductive film is provided which is an alloy film containing a metal in a proportion of 0.1 to 10 atomic% with respect to the total amount of silver.
そして、本発明の第７の発明によれば、樹脂フィルム基板の少なくとも一方の面に第１〜６の発明のいずれかの透明導電膜が形成されたことを特徴とする透明導電性フィルムが提供される。 And according to 7th invention of this invention, the transparent conductive film in which the transparent conductive film in any one of 1st- 6th invention was formed in the at least one surface of the resin film board | substrate is provided. Is done.
本発明の透明導電膜は耐湿性と耐薬品性を兼ね備え、１５Ω／□以下の高い導電性も実現可能である。しかも人体や環境に優しくて資源的にも豊富な材料を使用しているなどの利点もある。
本発明の透明導電膜や透明導電性フィルムは液晶ディスプレイ、エレクトロクロミックディスプレイ、エレクトロルミネッセンスディスプレイ、プラズマディスプレイ用などの透明電極以外に、熱線遮断膜、電磁波遮蔽膜、防曇ガラス用透明発熱体等に好適である。従って、本発明は産業上きわめて有用である。
The transparent conductive film of the present invention has both moisture resistance and chemical resistance, and can achieve high conductivity of 15Ω / □ or less. In addition, there are advantages such as using materials that are kind to the human body and the environment and are abundant in resources.
In addition to transparent electrodes for liquid crystal displays, electrochromic displays, electroluminescent displays, plasma displays, etc., the transparent conductive film and transparent conductive film of the present invention can be used for heat ray blocking films, electromagnetic wave shielding films, transparent heating elements for antifogging glass, etc. Is preferred. Therefore, the present invention is very useful industrially.
本発明の透明導電膜は、基本構造として、酸化物膜、金属膜、酸化物膜とがこの順に積層された透明導電膜において、酸化物膜として酸化物焼結体ターゲットを用いたスパッタリングにより形成されたａ−ＺＳＯ膜を用い、金属膜としてＡｇ若しくはＡｇを主成分とするものを用いるものである。そして、本発明の透明導電フィルムは、樹脂フィルム基板の少なくとも片面に本発明の透明導電膜が設けられたものである。 The transparent conductive film of the present invention is formed by sputtering using a sintered oxide target as an oxide film in a transparent conductive film in which an oxide film, a metal film, and an oxide film are laminated in this order as a basic structure. The a-ZSO film is used, and a metal film containing Ag or Ag as a main component is used. And the transparent conductive film of this invention is provided with the transparent conductive film of this invention in the at least single side | surface of the resin film board | substrate.
Ｚｎ−Ｓｎ−Ｏ系酸化物膜自体としては、特開平８−１７１８２４号公報でＺｎ2ＳｎＯ4化合物結晶、ＺｎＳｎＯ3化合物結晶を中心とした薄膜の技術が開示されている。しかし、これらはいずれも結晶質の薄膜であり、本発明のａ−ＺＳＯ膜とは特性等において大きく異なる。
また、Ｚｎ−Ｓｎ−Ｏ酸化物膜と金属膜との組み合わせでみると、特開平２−１４５４５８号公報に、Ｚｎ−Ｓｎ−Ｏ膜の上にＣｒＮ反射膜を積層した構造の太陽エネルギー反射性製品が提案されているが、本発明は、極薄Ａｇ若しくはＡｇを主成分とする金属膜をａ−ＺＳＯ膜で挟み込んだ構造の透明導電膜であり、大きく異なる。
As a Zn—Sn—O-based oxide film itself, JP-A-8-171824 discloses a technique of a thin film centered on a Zn 2 SnO 4 compound crystal and a ZnSnO 3 compound crystal. However, these are all crystalline thin films and are greatly different in characteristics and the like from the a-ZSO film of the present invention.
Further, in terms of a combination of a Zn—Sn—O oxide film and a metal film, Japanese Patent Application Laid-Open No. 2-145458 discloses solar energy reflectivity having a structure in which a CrN reflection film is laminated on a Zn—Sn—O film. Although a product has been proposed, the present invention is a transparent conductive film having a structure in which an ultra-thin Ag or a metal film mainly composed of Ag is sandwiched between a-ZSO films, and is greatly different.
まず図を用いて本発明の透明導電膜の構成を説明する。
図１は請求項１記載の透明導電膜例の断面図を示したものである。図１において、１と３はａ−ＺＳＯ膜であり、２は銀若しくは銀を主成分とする金属膜である。
First, the configuration of the transparent conductive film of the present invention will be described with reference to the drawings.
FIG. 1 shows a sectional view of an example of the transparent conductive film according to the first aspect. In FIG. 1, 1 and 3 are a-ZSO films, and 2 is silver or a metal film containing silver as a main component.
図２、図３は請求項２記載の透明導電膜例の断面図を示したものである。前記と同様に、１と３はａ−ＺＳＯ膜であり、２は銀若しくは銀を主成分とする金属膜である。そして、４，５はａ−ＺＳＯ膜と異なる酸化物膜である。 2 and 3 are sectional views of examples of the transparent conductive film according to the second aspect. Similarly to the above, 1 and 3 are a-ZSO films, and 2 is silver or a metal film containing silver as a main component. Reference numerals 4 and 5 are oxide films different from the a-ZSO film.
図４は請求項３記載の透明導電膜例の断面図を示したものである。前記と同様に、１と３と６とはａ−ＺＳＯ膜であり、２と７とは銀若しくは銀を主成分とする金属膜である。 FIG. 4 shows a sectional view of an example of the transparent conductive film according to the third aspect. Similarly to the above, 1, 3 and 6 are a-ZSO films, and 2 and 7 are silver or a metal film containing silver as a main component.
図５は請求項４記載の透明導電膜例の断面図を示したものであり、図２のものの上に図３のものを積層した構成となっている。１と３と６と８とはａ−ＺＳＯ膜であり、２と７とは銀若しくは銀を主成分とする金属膜であり、４と５と９とははａ−ＺＳＯ膜と異なる酸化物膜である。
以上の図において、１と３と６と８、または２と７、または４と５と９とを構成する材料は、それぞれ同一であっても良く、本発明の材料の範囲内で異なっていても良い。
FIG. 5 shows a cross-sectional view of an example of the transparent conductive film according to the fourth aspect, in which the structure shown in FIG. 3 is laminated on the structure shown in FIG. 1, 3, 6 and 8 are a-ZSO films, 2 and 7 are silver or a metal film containing silver as a main component, and 4, 5 and 9 are oxides different from the a-ZSO film. It is a membrane.
In the above figures, the materials constituting 1 and 3 and 6 and 8, or 2 and 7, or 4 and 5 and 9 may be the same or different within the scope of the material of the present invention. Also good.
次に各膜等について説明する。
・ａ−ＺＳＯ膜（図中の１、３、６、８）
本発明でａ−ＺＳＯ膜を用いるのは、該膜がＡｇ、若しくはＡｇを主要成分とする金属膜との高い密着性を有するからである。金属膜とその両面に設けられた酸化物膜との密着性が悪いと、湿気の影響で銀膜と酸化物膜の界面で剥離が生じ酸化物膜が破損し、銀などの金属膜に白色斑点が発生する。本発明のように、金属膜との高い密着性を有するａ−ＺＳＯ膜で金属膜を挟むことにより、得られる透明導電膜の耐湿性を向上できる。また、ａ−ＺＳＯ膜自体が高い耐薬品性を有するため、得られる透明導電膜の耐湿性と耐薬品性を向上させることができる。
Next, each film will be described.
A-ZSO film (1, 3, 6, 8 in the figure)
The reason why the a-ZSO film is used in the present invention is that the film has high adhesion to Ag or a metal film containing Ag as a main component. If the adhesion between the metal film and the oxide film provided on both sides of the metal film is poor, peeling will occur at the interface between the silver film and the oxide film due to moisture, and the oxide film will be damaged, and the metal film such as silver will be white. Spots appear. As in the present invention, the moisture resistance of the obtained transparent conductive film can be improved by sandwiching the metal film with an a-ZSO film having high adhesion to the metal film. In addition, since the a-ZSO film itself has high chemical resistance, the moisture resistance and chemical resistance of the obtained transparent conductive film can be improved.
本発明において、ａ−ＺＳＯ膜を用いるのは、例えば、ＺｎＯ結晶相、Ｚｎ2ＳｎＯ4結晶相、ＺｎＳｎＯ3結晶相、ＳｎＯ2結晶相などの結晶相が含まれていると、金属膜を覆っている酸化物膜中に粒界が存在することになり、粒界を介して大気中の水や酸素などのガスが拡散浸入して、挟み込んだ金属膜を腐食しやすくしてしまうからである。 In the present invention, the a-ZSO film is used because the metal film is covered when a crystal phase such as a ZnO crystal phase, a Zn 2 SnO 4 crystal phase, a ZnSnO 3 crystal phase, or a SnO 2 crystal phase is included. This is because there is a grain boundary in the oxide film, and gas such as water and oxygen in the atmosphere diffuses and penetrates through the grain boundary, making it easy to corrode the sandwiched metal film. .
ａ−ＺＳＯ膜は、ＳｎとＺｎの総和に対してＳｎを１０〜９０原子％含むことが必要である。Ｓｎが１０原子％未満では、耐薬品性が不充分となる。さらに５原子％以下ではＺｎＯ構造の結晶膜が得られやすくなり、非晶質構造がとりにくくなるからである。また９０原子％を越えると、ＳｎＯ２構造の結晶膜が得やすくなり、非晶質構造が得られにくくなってしまうからである。
The a-ZSO film needs to contain 10 to 90 atomic% of Sn with respect to the total of Sn and Zn. When Sn is less than 10 atomic%, the chemical resistance becomes insufficient. Further, if it is 5 atomic% or less, a ZnO structure crystal film is easily obtained, and an amorphous structure is difficult to be formed. On the other hand, if it exceeds 90 atomic%, it becomes easy to obtain a crystal film of SnO 2 structure and it becomes difficult to obtain an amorphous structure.
また、可視域の短波長側（波長３８０〜４００ｎｍ）の透過率を高めるために、ａ−ＺＳＯ膜は、ＧａとＡｌのうち少なくとも一方を該酸化物膜中の全金属の総和に対して５０原子％以下の割合で含有することが好ましい。特に、ＧａをＳｎ、Ｚｎ、Ｇａの総和に対して５０原子％以下の割合だけ含むことがより好ましい。 In order to increase the transmittance on the short wavelength side (wavelength 380 to 400 nm) in the visible range, the a-ZSO film has at least one of Ga and Al with respect to the sum of all metals in the oxide film. It is preferable to contain in the ratio of atomic% or less. In particular, it is more preferable that Ga is contained in an amount of 50 atomic% or less with respect to the total of Sn, Zn, and Ga.
Ｇａを５０原子％以下の割合で含ませることによって、ａ−ＺＳＯ膜の可視域短波長側（波長３８０〜４００ｎｍ付近）の吸収端が、更に短波長側にシフトし、波長３８０〜４００ｎｍ付近の透過率を改善することができる。しかしＧａが５０原子％を超えた割合で膜中に含有されると、膜の導電性が悪化して、例えば図１に示すような構造の金属膜との積層膜を作製しても、１５Ω／□以下の導電性を得ることができない。 By including Ga at a ratio of 50 atomic% or less, the absorption edge of the a-ZSO film on the short wavelength side in the visible range (near wavelength 380 to 400 nm) is further shifted to the short wavelength side, and near the wavelength 380 to 400 nm. The transmittance can be improved. However, if Ga is contained in the film in a proportion exceeding 50 atomic%, the conductivity of the film deteriorates, and even if a laminated film with a metal film having a structure as shown in FIG. / □ The following conductivity cannot be obtained.
ａ−ＺＳＯ膜の厚さは１ｎｍ以上とすることが好ましい。１ｎｍ未満では金属膜（特にＡｇを主成分とする膜）との密着性が不充分となるため耐湿性が不良となる。 The thickness of the a-ZSO film is preferably 1 nm or more. If it is less than 1 nm, the adhesion to a metal film (especially a film containing Ag as a main component) becomes insufficient, resulting in poor moisture resistance.
本発明におけるａ−ＺＳＯ膜は、生産性を考慮してスパッタリング法で作製する。酸化物膜の成膜法としては、酸化物焼結体ターゲットを用いてＡｒ雰囲気中もしくは酸化性ガスを少量添加したＡｒ雰囲気中でスパッタリングする方法と、金属ターゲットを用いて酸化性ガス・Ａｒガス混合雰囲気中でスパッタリングする方法とがあるが、ＺｎとＳｎを含む酸化物膜は前者の方法で作製する。後者の方法では金属膜にダメージを与えるため比抵抗が上昇するので好ましくない。 The a-ZSO film in the present invention is manufactured by a sputtering method in consideration of productivity. As a method for forming an oxide film, sputtering is performed in an Ar atmosphere using an oxide sintered compact target or in an Ar atmosphere to which a small amount of oxidizing gas is added, and an oxidizing gas / Ar gas using a metal target. There is a method of sputtering in a mixed atmosphere, but an oxide film containing Zn and Sn is formed by the former method. The latter method is not preferable because the specific resistance increases because the metal film is damaged.
・金属膜（図中の２、７）
本発明において金属膜を、Ａｇ若しくはＡｇを主成分とする合金で構成するのは、こうすることにより安価に低比抵抗で高可視光透過率の透明導電膜が得られるからである。なお、このＡｇを主成分とする合金膜とは、銀にパラジウム、金、白金、銅からなる群から選ばれる１種以上の金属を添加した合金膜を意味する。
・ Metal film (2, 7 in the figure)
In the present invention, the metal film is made of Ag or an alloy containing Ag as a main component because a transparent conductive film having a low specific resistance and a high visible light transmittance can be obtained at low cost. The alloy film containing Ag as a main component means an alloy film in which one or more metals selected from the group consisting of palladium, gold, platinum, and copper are added to silver.
銀のみで金属膜を構成しても良いが、環境に対する安定性向上の観点からパラジウム、金、白金、銅からなる群から選ばれる１種以上の金属と銀との合金膜であることが好ましい。 Although the metal film may be composed of only silver, it is preferably an alloy film of one or more metals selected from the group consisting of palladium, gold, platinum, and copper from the viewpoint of improving environmental stability. .
本発明の合金膜において、パラジウム、金、白金、銅からなる群から選ばれる１種以上の金属は、銀との合量に対して０．１〜１０原子％の割合で含まれることが好ましい。０．１原子％未満では耐久性が不充分となり、１０原子％を超えると可視光透過率の低下および高比抵抗化をもたらす。 In the alloy film of the present invention, it is preferable that one or more metals selected from the group consisting of palladium, gold, platinum, and copper are included in a proportion of 0.1 to 10 atomic% with respect to the total amount with silver. . If it is less than 0.1 atomic%, the durability is insufficient. If it exceeds 10 atomic%, the visible light transmittance is lowered and the specific resistance is increased.
金属膜の膜厚は、３〜２５ｎｍが好ましい。３ｎｍ未満ではシート抵抗が高くなり、２５ｎｍを超えると可視光透過率が低下する。金属膜は、金属ターゲットを用いてＡｒガス雰囲気中でスパッタリングすることで形成される。金属ターゲットは充分な導電性を有しているため、直流スパッタリングによる成膜が可能である。比抵抗調整や機械的耐久性向上の目的で雰囲気中にＮ2 などのガスを添加してもよい。 The thickness of the metal film is preferably 3 to 25 nm. When the thickness is less than 3 nm, the sheet resistance increases. When the thickness exceeds 25 nm, the visible light transmittance decreases. The metal film is formed by sputtering in an Ar gas atmosphere using a metal target. Since the metal target has sufficient conductivity, it can be formed by direct current sputtering. A gas such as N 2 may be added to the atmosphere for the purpose of adjusting specific resistance and improving mechanical durability.
・ａ−ＺＳＯ膜と異なる酸化物膜（図中の４、５、９）
機械的、化学的耐久性を向上させる目的で、ａ−ＺＳＯ膜の上にこれと異なる酸化物膜を設け、ａ−ＺＳＯ膜の保護層とすることもできる。
・ Oxide film different from a-ZSO film (4, 5, 9 in the figure)
For the purpose of improving mechanical and chemical durability, an oxide film different from this may be provided on the a-ZSO film to form a protective layer for the a-ZSO film.
この目的で用いる酸化物膜は、ａ−ＺＳＯ膜よりも高い導電性を有して耐薬品性に優れた酸化物膜であることが好ましい。例えば、Ｉｎ2 Ｏ3 、ＩＴＯ、ＩＣＯ、ＳｎＯ2 、ＴｉＯ2 、ＳｎとＺｎを含む結晶質酸化物等の材料が使用できる。このような酸化物膜を積層することで、積層体全体の導電性をさらに増加させることも可能である。 The oxide film used for this purpose is preferably an oxide film having higher conductivity than the a-ZSO film and excellent chemical resistance. For example, materials such as In 2 O 3 , ITO, ICO, SnO 2 , TiO 2 , crystalline oxide containing Sn and Zn can be used. By laminating such an oxide film, the conductivity of the entire stacked body can be further increased.
また、この酸化物膜としてａ−ＺＳＯ膜と屈折率が異なる材料を用いることにより、積層体の光学効果（反射防止など）を狙うことが可能である。この様な目的で利用する場合でも、耐薬品性に優れた酸化物膜であることが好ましい。この様な用途として、ＩＣＯ、ＴｉＯ2 、Ｎｂ2Ｏ5、Ｔａ2Ｏ5、ＳｉＯ2、Ａｌ2Ｏ3などの材料が使用できる。このような酸化物膜を積層することで、積層体全体の光反射特性や光透過特性を変性することができる。 In addition, by using a material having a refractive index different from that of the a-ZSO film as the oxide film, it is possible to aim at an optical effect (antireflection, etc.) of the stacked body. Even when used for such a purpose, an oxide film having excellent chemical resistance is preferable. For such applications, materials such as ICO, TiO 2 , Nb 2 O 5 , Ta 2 O 5 , SiO 2 , and Al 2 O 3 can be used. By stacking such oxide films, the light reflection characteristics and light transmission characteristics of the entire stack can be modified.
この酸化物膜の膜厚は、光学特性の観点から、最終的な透明導電膜の膜厚が１０〜１５０ｎｍとなるように調整することが好ましい。最終的な透明導電膜の厚さが１０ｎｍ未満および１５０ｎｍ超では可視光透過率が低下する。 The thickness of the oxide film is preferably adjusted so that the final transparent conductive film has a thickness of 10 to 150 nm from the viewpoint of optical characteristics. When the final thickness of the transparent conductive film is less than 10 nm and more than 150 nm, the visible light transmittance is lowered.
この酸化物膜を成膜するには、酸化物焼結体ターゲットを用いてＡｒ雰囲気中もしくは酸化性ガスを少量添加したＡｒ雰囲気中でスパッタリングする方法と、金属ターゲットを用いて酸化性ガス・Ａｒガス混合雰囲気中でスパッタリングする方法とがあるが、本発明では酸化物焼結体ターゲットを用いる方法で作製し、ターゲット材料コスト、生産性、生産安定性等を考慮する。なお、いずれの酸化物膜も、用いるターゲットが導電性を有しており、直流スパッタリングによる成膜が可能な場合は、生産性の観点から直流スパッタリングで成膜することが好ましい。 In order to form this oxide film, sputtering is performed in an Ar atmosphere using an oxide sintered compact target or in an Ar atmosphere to which a small amount of oxidizing gas is added, and an oxidizing gas / Ar using a metal target. There is a method of sputtering in a gas mixed atmosphere. In the present invention, a method using an oxide sintered compact target is used, and target material cost, productivity, production stability, and the like are taken into consideration. Note that in any oxide film, when the target to be used has conductivity and can be formed by DC sputtering, it is preferably formed by DC sputtering from the viewpoint of productivity.
・透明導電性フィルム
本発明の透明導電膜は、ガラス板、樹脂製フィルム、樹脂製板などの基体上に形成することができる。また、ガラス板などの上にカラー画素となるカラーフィルタ層を形成し、該カラーフィルタ層上に、カラーフィルタを保護、平滑化するための透明樹脂層を形成し、さらに該透明樹脂層上にシリカ、ＳｉＮx などの無機中間膜層（透明導電膜との密着改善層）を順次積層したものを基体として用いてもよい。
-Transparent conductive film The transparent conductive film of this invention can be formed on base | substrates, such as a glass plate, a resin film, and a resin board. Further, a color filter layer to be a color pixel is formed on a glass plate or the like, a transparent resin layer for protecting and smoothing the color filter is formed on the color filter layer, and further on the transparent resin layer A substrate in which an inorganic intermediate film layer (adhesion improving layer with a transparent conductive film) such as silica and SiN x is sequentially laminated may be used.
本発明の透明導電性フィルムは、樹脂フィルム基板の少なくとも一方の面に本発明のａ−ＺＳＯ膜を形成したものである。本発明に使用しうる樹脂フィルムは、ポリエチレンテレフタレート（ＰＥＴ）、ポリエーテルスルホン（ＰＥＳ）、ポリアリレート（ＰＡＲ）、ポリカーボネート（ＰＣ）、ポリエチレンナフタレート（ＰＥＮ）からなるか、もしくは、これらの材料の表面にアクリル系有機物などで代表されるハードコート層を覆った積層構造からなるのが好ましいが、これらに限定はしない。 The transparent conductive film of the present invention is obtained by forming the a-ZSO film of the present invention on at least one surface of a resin film substrate. The resin film that can be used in the present invention is made of polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate (PAR), polycarbonate (PC), polyethylene naphthalate (PEN), or of these materials. It is preferable to have a laminated structure with a hard coat layer typified by an acrylic organic material on the surface, but is not limited thereto.
樹脂フィルム基板は、ガラス板と比べてガスの透過性が高く、有機ＥＬ素子の発光層、およびＬＣＤなどの液晶層は、水分や酸素に対して劣化するため、これらの表示素子の基板として用いる場合は、ガスの通過を抑えるガスバリア膜を施すことが好ましい。 The resin film substrate has higher gas permeability than the glass plate, and the light emitting layer of the organic EL element and the liquid crystal layer of the LCD or the like deteriorate with respect to moisture and oxygen, and therefore are used as a substrate for these display elements. In this case, it is preferable to apply a gas barrier film that suppresses the passage of gas.
ガスバリア膜は、樹脂フィルムの片面に形成されていても良く、両面に形成されていれば、ガス通過の遮断性はさらに良好となる。また、ガスバリア膜を、樹脂フィルムの片面に形成し、さらに該ガスバリア膜の上に、樹脂フィルムを積層することによって、内部にガスバリア膜を挿入させた構成を得ることができる。さらに、複数回、積層を繰り返した構造とすることもできる。 The gas barrier film may be formed on one surface of the resin film, and if it is formed on both surfaces, the gas passage blocking property is further improved. Moreover, the structure which inserted the gas barrier film | membrane inside can be obtained by forming a gas barrier film | membrane on the single side | surface of a resin film, and also laminating | stacking a resin film on this gas barrier film | membrane. Furthermore, it can also be set as the structure which repeated lamination | stacking several times.
ガスバリア膜は、酸化シリコン膜、酸化窒化シリコン（ＳｉＯＮ）膜、アルミニウム酸マグネシウム膜、酸化スズ系膜およびダイヤモンド状カーボン（ＤＬＣ）膜の中から選ばれる少なくとも１種類であることが好ましい。ここで、酸化スズ系膜とは、酸化スズに、例えば、Ｓｉ、Ｃｅ、Ｇｅなどから選ばれる少なくとも１種類以上の添加元素を含有した組成を有する。これらの添加元素によって、酸化スズ層を非晶質化し、緻密な膜とする。 The gas barrier film is preferably at least one selected from a silicon oxide film, a silicon oxynitride (SiON) film, a magnesium aluminate film, a tin oxide film, and a diamond-like carbon (DLC) film. Here, the tin oxide film has a composition containing at least one additional element selected from, for example, Si, Ce, Ge and the like in tin oxide. By these additive elements, the tin oxide layer is made amorphous to form a dense film.
また、酸化シリコン膜、酸化窒化シリコン膜、アルミニウム酸マグネシウム膜、酸化スズ系膜およびダイヤモンド状カーボン膜の中から選ばれる少なくとも１種類のガスバリア膜と、有機もしくは高分子の膜とが、樹脂基板もしくは樹脂フィルムの表面に交互に繰り返し積層させた構造の基板上に、前記透明導電性薄膜を施した構成でもよい。
なお、本発明の透明導電膜は成膜後、非晶質性を維持できる範囲内で、加熱処理されてもよい。加熱処理により、低抵抗化、高可視光透過率化、耐久性向上が期待できる。
Further, at least one gas barrier film selected from a silicon oxide film, a silicon oxynitride film, a magnesium aluminum oxide film, a tin oxide film, and a diamond-like carbon film, and an organic or polymer film may be a resin substrate or The structure which gave the said transparent conductive thin film on the board | substrate of the structure laminated | stacked alternately on the surface of the resin film may be sufficient.
The transparent conductive film of the present invention may be heat-treated within a range in which amorphousness can be maintained after film formation. Heat treatment can be expected to reduce resistance, increase visible light transmittance, and improve durability.
（実施例１〜２０）
成膜
ガラス基板もしくは樹脂フィルム基板の透明基体上に、表１の実施例１〜２０に示す構成の透明導電膜を直流スパッタリング法により形成した。ガラス基板は低アルカリガラス（コーニング社製＃７０５９、厚み１．１ｍｍｔ）、樹脂フィルム基板には東洋紡製のＰＥＴフィルム（コスモシャインＡ４３００、厚み１００μｍｔ）を用いた。表１の膜構成欄内の下の（ ）内の数字は膜厚（ｎｍ）である。
Ｉｎ２Ｏ３膜は、Ｉｎ２Ｏ３焼結体ターゲットを用い、２体積％酸素を含んだＡｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。
ＩＴＯ膜は、ＳｎとＩｎの総和に対してＳｎを１０原子％含むＩｎ２Ｏ３焼結体ターゲットを用い、２体積％酸素を含んだＡｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。成膜後のＩＴＯ膜の組成は、用いたターゲットの組成と同一であった。
ａ−ＺＳＯ膜は、ＺｎとＳｎの酸化物焼結体ターゲットから直流スパッタリング法で作製した。Ａｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。成膜後のａ−ＺＳＯ膜の組成は、用いたターゲットの組成と同一であることをＩＣＰ発光分光分析で確認した。またａ−ＺＳＯ膜は非晶質構造であることをＸ線回折測定で確認した。なお、Ｚｎ、Ｓｎの総和に対する膜中のＳｎ含有量をｘ原子％として、得られた膜をａ−ＺＳＯ（ｘ）で示す。ここで「ａ−」はアモルファスを意味する（その逆として、「ｃ−」は結晶膜を意味する）。
Ｇａ２Ｏ３を添加したＺｎとＳｎを含む非晶質酸化物膜（以下ａ−ＧＺＳＯ膜と略す）は、Ｇａ２Ｏ３を添加したＺｎとＳｎの酸化物焼結体ターゲットから、室温基板上に直流スパッタリング法で作製した。Ａｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより成膜した。成膜後のａ−ＧＺＳＯ膜の組成は、用いたターゲットの組成と同一であることをＩＣＰ発光分光分析で確認した。またＧＳＮ膜は非晶質構造であることをＸ線回折測定で確認した。なお、Ｚｎ、Ｓｎの総和に対する膜中のＳｎ含有量をｘ原子％、Ｚｎ、Ｓｎ、Ｇａの総和に対する膜中のＧａ含有量をｙ原子％として、得られた膜をａ−ＧＺＳＯ（ｘ、ｙ）で示す。ここで「ａ−」はアモルファスを意味する。
Ａｌ２Ｏ３を添加したＺｎとＳｎを含む非晶質酸化物膜（以下ａ−ＡＺＳＯ膜と略す）は、Ａｌ２Ｏ３を添加したＺｎとＳｎの酸化物焼結体ターゲットから、室温基板上に直流スパッタリング法で作製した。Ａｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより成膜した。成膜後のａ−ＡＺＳＯ膜の組成は、用いたターゲットの組成と同一であることをＩＣＰ発光分光分析で確認した。またＡＳＮ膜は非晶質構造であることをＸ線回折測定で確認した。なお、Ｚｎ、Ｓｎの総和に対する膜中のＳｎ含有量をｘ原子％、Ｚｎ、Ｓｎ、Ａｌの総和に対する膜中のＡｌ含有量をｙ原子％として、得られた膜をａ−ＡＺＳＯ（ｘ、ｙ）で示す。ここで「ａ−」はアモルファスを意味する。
ＡｇＰｄ膜は、Ｐｄ１原子％含むＡｇ−Ｐｄ合金ターゲットを用い、Ａｒガス２ｍＴｏｒｒの雰囲気中、０．５５Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。成膜後のＡｇＰｄ膜の組成は、用いたターゲットの組成と同一であった。
ＡｇＡｕＣｕ膜は、Ａｕ１原子％とＣｕ０．５原子％含むＡｇ−Ａｕ−Ｃｕ合金ターゲットを用い、Ａｒガス２ｍＴｏｒｒの雰囲気中、０．５５Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。成膜後のＡｇＡｕＣｕ膜の組成は、用いたターゲットの組成と同一であった。
Ａｇ膜は、純度４ＮのＡｇターゲットを用い、Ａｒガス２ｍＴｏｒｒの雰囲気中、０．５５Ｗ／ｃｍ２の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。
(Examples 1-20)
A transparent conductive film having a structure shown in Examples 1 to 20 in Table 1 was formed on a transparent substrate of a film- forming glass substrate or a resin film substrate by a direct current sputtering method. The glass substrate was low alkali glass (# 7059 manufactured by Corning, thickness 1.1 mmt), and the resin film substrate was a Toyobo PET film (Cosmo Shine A4300, thickness 100 μmt). The number in () below the film configuration column in Table 1 is the film thickness (nm).
The In 2 O 3 film is obtained by subjecting an In 2 O 3 sintered body target to direct current sputtering at an electric power density of 2.2 W / cm 2 in an atmosphere of 0.6 Pa of Ar gas containing 2 volume% oxygen. A film was formed on a room temperature substrate.
The ITO film uses an In 2 O 3 sintered body target containing 10 atomic% of Sn with respect to the sum of Sn and In, and is 2.2 W / cm in an atmosphere of 0.6 Pa of Ar gas containing 2 volume% oxygen. The film was formed on a room temperature substrate by direct current sputtering at a power density of 2 . The composition of the ITO film after film formation was the same as the composition of the target used.
The a-ZSO film was formed by a direct current sputtering method from an oxide sintered compact target of Zn and Sn. A film was formed on a room temperature substrate by direct current sputtering at an electric power density of 2.2 W / cm 2 in an atmosphere of Ar gas of 0.6 Pa. It was confirmed by ICP emission spectroscopic analysis that the composition of the a-ZSO film after film formation was the same as the composition of the target used. The a-ZSO film was confirmed by X-ray diffraction measurement to have an amorphous structure. The obtained film is represented by a-ZSO (x), where the Sn content in the film with respect to the sum of Zn and Sn is x atomic%. Here, “a−” means amorphous (conversely, “c−” means crystal film).
An amorphous oxide film containing Zn and Sn to which Ga 2 O 3 is added (hereinafter abbreviated as a-GZSO film) is formed from a Zn and Sn oxide sintered body target to which Ga 2 O 3 is added from a room temperature substrate. It was produced by direct current sputtering. The film was formed by direct current sputtering at an electric power density of 2.2 W / cm 2 in an atmosphere of Ar gas of 0.6 Pa. It was confirmed by ICP emission spectroscopic analysis that the composition of the a-GZSO film after film formation was the same as the composition of the target used. The GSN film was confirmed by X-ray diffraction measurement to have an amorphous structure. Note that the Sn content in the film with respect to the sum of Zn and Sn is x atomic%, and the Ga content in the film with respect to the sum of Zn, Sn, and Ga is y atomic%, and the obtained film is a-GZSO (x, y). Here, “a−” means amorphous.
An amorphous oxide film containing Zn and Sn to which Al 2 O 3 is added (hereinafter abbreviated as a-AZSO film) is obtained from a Zn and Sn oxide sintered body target to which Al 2 O 3 is added from a room temperature substrate. It was produced by direct current sputtering. The film was formed by direct current sputtering at an electric power density of 2.2 W / cm 2 in an atmosphere of Ar gas of 0.6 Pa. It was confirmed by ICP emission spectroscopic analysis that the composition of the a-AZSO film after film formation was the same as the composition of the target used. The ASN film was confirmed by X-ray diffraction measurement to have an amorphous structure. Note that the Sn content in the film with respect to the sum of Zn and Sn is x atomic%, and the Al content in the film with respect to the sum of Zn, Sn, and Al is y atomic%, and the resulting film is a-AZSO (x, y). Here, “a−” means amorphous.
The AgPd film was formed on a room temperature substrate by direct current sputtering at an electric power density of 0.55 W / cm 2 in an atmosphere of Ar gas 2 mTorr using an Ag—Pd alloy target containing 1 atomic% of Pd. The composition of the AgPd film after film formation was the same as the composition of the target used.
The AgAuCu film is formed on a substrate at room temperature by direct current sputtering at an electric power density of 0.55 W / cm 2 in an atmosphere of Ar gas 2 mTorr using an Ag—Au—Cu alloy target containing 1 atomic% of Au and 0.5 atomic% of Cu. A film was formed. The composition of the AgAuCu film after film formation was the same as the composition of the target used.
The Ag film was formed on a room temperature substrate by direct current sputtering at a power density of 0.55 W / cm 2 in an Ar gas 2 mTorr atmosphere using an Ag target having a purity of 4N.
透明導電性膜の評価
耐湿性については、７０℃、湿度９０％の雰囲気中に１週間放置するという耐湿試験を行った後、直径０．５ｍｍ以上の白色斑点が発生しなかったサンプルを○、直径１ｍｍ以上の白色斑点が発生したサンプルを×と判定した。
耐アルカリ性については、室温の１重量％ＮａＯＨ水溶液中に２０分間浸けるという耐アルカリ試験を行った後、膜に変化が見られなかったサンプルを○、変色等の劣化が見られたものを×と判定した。
各構成の透明導電膜のシート抵抗は、四探針法により測定した。
表１に、各構成の透明導電膜のシート抵抗の測定結果、耐湿性および耐アルカリ性の評価結果を示す。表１中の実施例１〜１４は図１の構造の透明導電膜であり、実施例１５は図２の構造の透明導電膜、実施例１６は図３の構造の透明導電膜、実施例１７は図４の構造の透明導電膜、実施例１８〜２０は図５の構造の透明導電膜の一例である。また実施例１１、１２、１６、１８は樹脂フィルム基板上に透明導電膜を形成しており、本発明の透明導電性フィルムである。実施例１〜２０の透明導電膜をＦＩＢ加工により薄片にして、断面構造を透過型電子顕微鏡による観察、電子線回折による膜構造の解析を行ったところ、作製したa-ＺＳＯ膜、a-ＡＺＳＯ膜、a-ＧＺＳＯ膜は全て非晶質膜になっていることを確認した。
Regarding the evaluation moisture resistance of the transparent conductive film, a sample in which white spots having a diameter of 0.5 mm or more did not occur after performing a moisture resistance test of leaving in an atmosphere of 70 ° C. and 90% humidity for 1 week A sample in which white spots with a diameter of 1 mm or more were generated was judged as x.
Regarding the alkali resistance, after performing an alkali resistance test of immersion in a 1% by weight NaOH aqueous solution at room temperature for 20 minutes, a sample in which no change was observed in the film was indicated as ◯, and deterioration such as discoloration was indicated as ×. Judged.
The sheet resistance of the transparent conductive film of each configuration was measured by a four probe method.
Table 1 shows the measurement results of the sheet resistance, the moisture resistance and the alkali resistance evaluation results of the transparent conductive film of each configuration. Examples 1 to 14 in Table 1 are transparent conductive films having the structure of FIG. 1, Example 15 is a transparent conductive film having the structure of FIG. 2, Example 16 is a transparent conductive film having the structure of FIG. 4 is an example of the transparent conductive film having the structure of FIG. 4, and Examples 18 to 20 are examples of the transparent conductive film having the structure of FIG. In Examples 11, 12, 16, and 18, a transparent conductive film is formed on a resin film substrate, and the transparent conductive film of the present invention. The transparent conductive films of Examples 1 to 20 were made into thin pieces by FIB processing, and the cross-sectional structure was observed with a transmission electron microscope and the film structure was analyzed by electron diffraction. As a result, the produced a-ZSO films and a-AZSO It was confirmed that the film and the a-GZSO film were all amorphous.
ａ−ＺＳＯ膜を用た実施例５と、a−ＧＺＳＯ膜を用いた実施例７〜９を比較すると、波長３８０〜４００ｎｍにおける透過率は実施例７〜９の方が１０〜１５％ほど改善されて高く、その改善幅はＧａ量が多いほど顕著であった。
表１に示すように、本発明の構造の実施例１〜２０の透明導電膜は耐湿性、耐アルカリ性共に良好であり、シート抵抗も１５Ω／□未満であり高い導電性を有していた。よって、プラズマディスプレイの電磁波遮蔽フィルターや液晶ディスプレイの透明電極などにも利用可能であるといえる。
Comparing Example 5 using the a-ZSO film and Examples 7 to 9 using the a-GZSO film, the transmittance at wavelengths of 380 to 400 nm is improved by 10 to 15% in Examples 7 to 9 The improvement was more remarkable as the amount of Ga increased.
As shown in Table 1, the transparent conductive films of Examples 1 to 20 having the structure of the present invention had good moisture resistance and alkali resistance, and had a sheet resistance of less than 15Ω / □ and high conductivity. Therefore, it can be said that it can be used for an electromagnetic wave shielding filter of a plasma display, a transparent electrode of a liquid crystal display, and the like.
（比較例１〜９）
ターゲット組成だけを変えて作製した、本発明の組成範囲を逸脱したＺＳＯ膜、ＧＺＳＯ膜、ＡＺＳＯ膜を用いて、表２に示す構造の透明導電膜を作製した。使用したガラス基板、樹脂フィルム基板は実施例と同じであり、Ｉｎ2Ｏ3膜、ＩＴＯ膜は、実施例と同じ条件で作製した。
ＧＺＯ膜は以下の手順で作製した。ＧａをＧａとＺｎの総和に対して５．０原子％含むＺｎＯ焼結体ターゲットを用い、Ａｒガス０．６Ｐａの雰囲気中、２．２Ｗ／ｃｍ2 の電力密度で直流スパッタリングすることにより、室温基板上に成膜した。成膜後のＧＺＯ膜の組成は、用いたターゲットの組成と同一であった。各膜の結晶性は、実施例と同様に断面片の透過型電子顕微鏡による観察と電子線回折により評価した。
表２に、実施例と同じ条件による、各構成の透明導電膜のシート抵抗の測定結果、耐湿性および耐アルカリ性の評価結果を示す。
(Comparative Examples 1-9)
Using a ZSO film, a GZSO film, and an AZSO film that were manufactured by changing only the target composition and deviated from the composition range of the present invention, a transparent conductive film having a structure shown in Table 2 was prepared. The glass substrate and resin film substrate used were the same as in the example, and the In 2 O 3 film and the ITO film were produced under the same conditions as in the example.
The GZO film was produced by the following procedure. Using a ZnO sintered body target containing Ga at 5.0 atomic% with respect to the sum of Ga and Zn, DC sputtering was performed at a power density of 2.2 W / cm 2 in an Ar gas 0.6 Pa atmosphere at room temperature. A film was formed on the substrate. The composition of the GZO film after film formation was the same as the composition of the target used. The crystallinity of each film was evaluated by observation of a cross-sectional piece with a transmission electron microscope and electron diffraction as in the example.
In Table 2, the measurement result of the sheet resistance of the transparent conductive film of each structure on the same conditions as an Example, the evaluation result of moisture resistance and alkali resistance are shown.
表２に示すように、比較例１〜３の透明導電膜は耐湿性で劣っていた。これは、Ａｇ系膜を覆っているＩｎ2Ｏ3膜とＩＴＯ膜の耐湿性が劣るからである。比較例４〜５の透明導電膜は、耐湿性は良好だったが、耐アルカリ性が劣っていた。これはＧＺＯ膜、ａ−ＺＳＯ膜自体の耐アルカリ性が劣っているからである。比較例５のａ−ＺＳＯ膜はＳｎ含有量が本発明で規定した割合よりも少ないため耐アルカリ性に劣っているのである。また比較例６、８、９は、耐湿性、耐アルカリ性共に劣っていた。
ここでＡｇ系薄膜を挟んでいるＺＳＯ膜、ＧＺＳＯ膜、ＡＺＳＯ膜は、Ｓｎ量が本発明で規定している割合を逸脱しているため、スパッタリング法で非晶質膜が得られなかった。結晶膜には粒界があり、粒界を介して水分がＡｇ系薄膜へ進入し腐食が起きて耐湿性を悪化させたのである。比較例６、８、９の耐アルカリ性が悪いのは、ＺＳＯ膜、ＧＺＳＯ膜、ＡＺＳＯ膜自体の耐アルカリ性が、膜中のＳｎ含有量が少ないため劣っているからである。比較例７は、耐アルカリ性は良好だが、耐湿性が悪かった。ここで用いられているＺＳＯ膜は、Ｓｎ含有量が多すぎて結晶膜となっており、粒界を介して水分がＡｇ系薄膜へ進入し腐食が起きて耐湿性を悪化させたのである。
比較例１〜９のような透明導電膜は、シート抵抗が低いが、耐湿性、耐アルカリ性に劣るため、プラズマディスプレイの電磁波遮蔽フィルターや液晶ディスプレイの透明電極などにも利用できない。
As shown in Table 2, the transparent conductive films of Comparative Examples 1 to 3 were inferior in moisture resistance. This is because the In 2 O 3 film and the ITO film covering the Ag-based film have poor moisture resistance. The transparent conductive films of Comparative Examples 4 to 5 had good moisture resistance but were inferior in alkali resistance. This is because the alkali resistance of the GZO film and the a-ZSO film itself is inferior. The a-ZSO film of Comparative Example 5 is inferior in alkali resistance because the Sn content is less than the ratio defined in the present invention. Further, Comparative Examples 6, 8, and 9 were inferior in both moisture resistance and alkali resistance.
Here, the ZSO film, the GZSO film, and the AZSO film sandwiching the Ag-based thin film had an amount of Sn deviating from the ratio defined in the present invention, and thus an amorphous film could not be obtained by the sputtering method. There is a grain boundary in the crystal film, and moisture enters the Ag-based thin film through the grain boundary, causing corrosion to deteriorate the moisture resistance. The reason why the alkali resistance of Comparative Examples 6, 8, and 9 is poor is that the alkali resistance of the ZSO film, the GZSO film, and the AZSO film itself is inferior because the Sn content in the film is small. In Comparative Example 7, the alkali resistance was good, but the moisture resistance was bad. The ZSO film used here is a crystalline film with too much Sn content, and moisture enters the Ag-based thin film through the grain boundary, causing corrosion and deteriorating moisture resistance.
Although the transparent conductive film like Comparative Examples 1-9 has low sheet resistance, since it is inferior to moisture resistance and alkali resistance, it cannot be utilized for the electromagnetic wave shielding filter of a plasma display, the transparent electrode of a liquid crystal display, etc.
（比較例１０〜１２）
表３に示すような構成の透明導電膜を作製した。ＺＳＯ膜、ＧＺＳＯ膜の成膜は、成膜時に基板を３００℃に加熱した以外は実施例と同様の条件で作製した。各膜の結晶性は、実施例と同様に断面片の透過型電子顕微鏡による観察と電子線回折により評価した。基板を３００℃に加熱して成膜して得られたＺＳＯ膜、ＧＺＳＯ膜は、Ｚｎ2ＳｎＯ4の結晶性化合物（ＪＣＰＤＳカードのＮｏ．２４−１４７０）や、ＺｎＳｎＯ3（ＪＣＰＤＳカードのＮｏ．５２−１３８１）の結晶性化合物が生成されていることがＸ線回折測定で明らかとなった。
表３に、実施例と同じ条件による、各構成の透明導電膜のシート抵抗の測定結果、耐湿性および耐アルカリ性の評価結果を示す。
(Comparative Examples 10-12)
A transparent conductive film having a structure as shown in Table 3 was produced. The ZSO film and the GZSO film were formed under the same conditions as in the examples except that the substrate was heated to 300 ° C. during the film formation. The crystallinity of each film was evaluated by observation of a cross-sectional piece with a transmission electron microscope and electron diffraction as in the example. The ZSO film and the GZSO film obtained by heating the substrate to 300 ° C. are formed of Zn 2 SnO 4 crystalline compound (JCPDS card No. 24-1470) or ZnSnO 3 (JCPDS card No. 24). X-ray diffraction measurement revealed that a crystalline compound of 52-1381) was produced.
Table 3 shows the sheet resistance measurement results, moisture resistance, and alkali resistance evaluation results of the transparent conductive films of the respective configurations under the same conditions as in the examples.
表３に示すように、比較例１０〜１２の透明導電膜は耐アルカリ性は良かったが、耐湿性で劣っていた。これは、Ａｇ系薄膜を挟んでいるＺＳＯ膜、ＧＺＳＯ膜は上述のように結晶膜を含んでおり、粒界を介して水分がＡｇ系薄膜へ進入し腐食が起きて耐湿性を悪化させたのである。
比較例１０〜１２のような透明導電膜は、シート抵抗が低いが、耐湿性、耐アルカリ性に劣るため、プラズマディスプレイの電磁波遮蔽フィルターや液晶ディスプレイの透明電極などにも利用できない。
As shown in Table 3, the transparent conductive films of Comparative Examples 10 to 12 had good alkali resistance but were inferior in moisture resistance. This is because the ZSO film and the GZSO film sandwiching the Ag-based thin film include the crystal film as described above, and moisture enters the Ag-based thin film through the grain boundary, which causes corrosion and deteriorates moisture resistance. It is.
Although the transparent conductive film like Comparative Examples 10-12 has low sheet resistance, since it is inferior to moisture resistance and alkali resistance, it cannot be utilized for the electromagnetic wave shielding filter of a plasma display, the transparent electrode of a liquid crystal display, etc.
１、３、６、８：ａ−ＺＳＯ膜
２、７：金属膜
４、５、９：ａ−ＺＳＯ膜でない酸化物膜
1, 3, 6, 8: a-ZSO film 2, 7: metal film 4, 5, 9: oxide film that is not an a-ZSO film
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